CN101487134A - Method for modulating zinc-nickel alloy and nickel combined multi-layer membranous by electrochemical deposition component - Google Patents
Method for modulating zinc-nickel alloy and nickel combined multi-layer membranous by electrochemical deposition component Download PDFInfo
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- CN101487134A CN101487134A CNA2009100762521A CN200910076252A CN101487134A CN 101487134 A CN101487134 A CN 101487134A CN A2009100762521 A CNA2009100762521 A CN A2009100762521A CN 200910076252 A CN200910076252 A CN 200910076252A CN 101487134 A CN101487134 A CN 101487134A
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Abstract
The invention provides a method for modulating a multilayer film consisting of Zn-Ni alloy and Ni by electro-chemically depositing compositions, comprising five steps as follows: preparing alkaline liquor, pickling liquor and electroplating solution, mechanical grinding and cleaning plating articles, alkaline washing, pickling and electroplating, wherein, the electroplating solution comprises alkaline electroplating solution with electroplated Zn-Ni alloy and neutral and alkaline electroplating solution with electroplated Ni; the electroplating solution of Ni consists essentially of a main salt and a complexing agent; the main salt is one or two compositions out of NiSO4 and NiCl2; and the complexing agent consists of two or more substances as follows: ammonium citrate, sodium citrate, citric acid, ammonia, sodium pyrophosphate, potassium pyrophosphate and triethanolamine. The Zn-Ni/Ni or Ni/Zn-Ni multilayer film electroplated by the method has smooth plating layer surface, better corrosion resistance and higher current efficiency and plating layer adhesion.
Description
Technical field
The invention belongs to the electroplating technology field in the Materials science, specifically, be meant the method for electrochemical deposition component modulation Zn-Ni/Ni or Ni/Zn-Ni multilayer film.
Background technology
The compositional modulation multilayer film is a kind of sandwich, it alternately stack up by the thin-film material of two kinds of metal or alloy and form form or structure on be periodically variable type material.In multilayer film, claim that single thin layer is sublayer or subgrade, the thickness sum that claims adjacent two thin layers is modulation wavelength or periodic thickness (representing with λ).From 70 years 20th century, more and more about compositional modulation multilayer film preparation, but up to the mid-90 in 20th century with the research report of performance, be that the scientists of representative just begins one's study and prepares the anti-corrosion behavior of compositional modulation multilayer film with electrodip process with Gabe.Most results of study show: the compositional modulation multilayer film has better solidity to corrosion than the single coating of same thickness.The preparation method of compositional modulation multilayer film can be divided into vapour deposition process and electrochemical method.Vapour deposition process is to the equipment requirements height, and preparation time is long, and cost is also high, so most researchers is selected the method for electrochemical deposition for use.The method of electrochemical deposition is promptly electroplated, and its equipment is simple, easy handling, and production cost is low, can carry out galvanic deposit on big area and complex-shaped matrix, and the coating deposition is fast, the production efficiency height.Have research at present, studies show that the solidity to corrosion of metal multilayer film is better than the single Zn or the Zn-Ni layer of same thickness the compositional modulation multilayer film of electroplating Zn/Ni, Zn/Zn-Ni etc.
Summary of the invention
The purpose of this invention is to provide the method that a kind of electrochemical deposition technique prepares Zn-Ni/Ni or Ni/Zn-Ni multilayer film.Zn-Ni/Ni or Ni/Zn-Ni multilayer film are the multilayer film of admiro and nickel combination, and difference is that the Zn-Ni/Ni multilayer film is an electroplating Zn-Ni alloy on matrix at first, re-plating Ni, at last with Ni as surface layer; The Ni/Zn-Ni multilayer film then is an electroplated Ni on matrix at first, the re-plating Zn-Ni alloy, at last with Zn-Ni alloy as surface layer.
The Zn-Ni/Ni or the Ni/Zn-Ni multilayer film that prepare by the inventive method have coating outward appearance, high anti-corrosion and the good bonding force of light.Described preparation method comprises the steps:
The first step, preparation alkaline wash, pickle solution and electroplate liquid.
Alkaline wash is to contain NaOH, Na
3PO
412H
2O, Na
2CO
310H
2O, Na
2SiO
3NH
2The aqueous solution of O wherein contains NaOH 60～80g, Na in every liter of alkaline wash
3PO
412H
2O 20～40g, Na
2CO
310H
2O20～40g, Na
2SiO
3NH
2O 20～40g, all the other are water.
Pickle solution adopts HCl solution, and to contain HCl in every liter of pickle solution be 4～8mL.
Alkalescence Zn-Ni alloy electroplating liquid is for containing ZnO, NiSO
4, NaOH, complexing agent, additive and brightening agent the aqueous solution, in every liter of plating bath, contain ZnO 10～30g, NiSO
45～13g, NaOH 100～140g contains an amount of complexing agent, additive and brightening agent and water in addition.
The electroplate liquid of electroplated Ni mainly is made up of main salt and complexing agent.Described main salt is NiSO
4And NiCl
2In one or both.The content that needs main salt in the plating bath is (containing in every liter of plating bath): NiSO
4100～350g or NiCl
2Among 10～300g one or both.Described complexing agent is to be made up of two or more the material in ammonium citrate, Trisodium Citrate, citric acid, ammoniacal liquor, trisodium phosphate, potassium pyrophosphate and the trolamine.The complexing agent components contents of required interpolation in plating bath is (containing in every liter of plating bath): ammonium citrate 40～60g, perhaps Trisodium Citrate 150～200g, perhaps citric acid 10～30g, perhaps ammoniacal liquor 30～150ml, perhaps trisodium phosphate 40～100g, perhaps potassium pyrophosphate 50～150g, perhaps two kinds among trolamine 10～40ml or two or more.Other added ingredientss are one or more in ammonium sulfate, sodium-chlor, sal epsom, the S-WAT.
The content that also contains added ingredients in the electroplate liquid of described electroplated Ni is (containing in every liter of plating bath): ammonium sulfate 40～60g, sodium-chlor 10～30g, sal epsom 10～60g, one or more among S-WAT 5～20g.
In second step, mechanical grinding is cleaned plating piece.
Plating piece is carried out mechanical grinding on aluminum oxide sandpaper, clean with organic solvent or aqueous cleaning agent then.Described organic solvent or aqueous cleaning agent are used to remove the greasy dirt of matrix surface, and organic solvent can be chosen trichloroethane, gasoline, and acetone, ethanol, trieline, a kind of arbitrarily in the tetracol phenixin, and adopt more than the ultrasonic cleaning matrix surface 10min.
The 3rd step, alkali cleaning.
The alkaline wash that plating piece after second step cleaned immerses the first step preparation carries out alkali cleaning, and the temperature of alkali cleaning is 70～90 ℃, behind time 10～20min with plating piece successively via mobile hot water wash, mobile cold wash;
The 4th step, pickling.
To carry out pickling through the plating piece after the 3rd step alkali cleaning, 15～30 ℃ of pickle solution temperature, scavenging period 0.5～1.0min takes out after the via flow cold wash.
In the 5th step, electroplate.
Described electroplating Zn-Ni/Ni comprises electroplating Zn-Ni alloy coating and Ni coating, and concrete steps are as follows:
(a) will be immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the first step through the 4th plating piece of step after the pickling and electroplate, electroplate after washing.The condition of electroplating Zn-Ni alloy coating is current density 1～6A/dm
2, 10～35 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.Under the constant condition of other processing condition, galvanized current density is big more, and thickness of coating is thick more.
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the plating bath of the electroplated Ni for preparing in the step 1 and electroplate, electroplate after washing.The condition of electroplated Ni coating is current density 0.5～3A/dm
2, pH value 7～9,25～65 ℃ of temperature.Under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.Under the constant condition of other processing condition, galvanized current density is big more, and thickness of coating is thick more.Under the constant situation of other processing condition, temperature is high more, and coating is thick more.
(c) repeating step (a)～(b) satisfies the multiplicity requirement up to Zn-Ni/Ni coating, dries up coating at last.
If electroplated Ni/Zn-Ni coating comprises electroplated Ni and Zn-Ni alloy coating, then at first will in being immersed in the plating bath of the electroplated Ni for preparing in the first step, electroplate the 4th plating piece of step after the pickling, electroplate after washing.Then the plating piece after the above-mentioned washing is immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the step 1, repeat electroplated Ni layer again after the washing washing then, so circulation is satisfied the multiplicity requirement up to Ni/Zn-Ni coating, dries up coating at last.
The invention has the advantages that:
(1) Zn-Ni alloy coating in the multilayer film of present Zn and Ni, Zn and Zn-Ni or Zn-Ni and Ni composition adopts acidic bath to make more, the compositional modulation Zn-Ni/Ni of the present invention's preparation or the Zn-Ni alloy coating in the Ni/Zn-Ni multilayer film adopt alkali plating solution to make, to compare coating more smooth with the compositional modulation multilayer film that Ni coating and the Zn-Ni coating that obtains in acid electroplating liquid are formed, and the composition of Zn-Ni alloy coating is even, thereby has improved solidity to corrosion.
(2) electroplate in compositional modulation Zn-Ni/Ni or the Ni/Zn-Ni multilayer film technology, electroplating Zn-Ni alloy coating adopts the alkali zinc nickel alloy plating process, solved in the acid technology with current density change coating interalloy composition variation problem greatly, and coating smooth, nickel content is 10%～15%, and coating is single γ phase, compares with general alkali plating solution, the current efficiency height of negative electrode reaches 80～90%.
(3) electroplated Ni also adopts neutrality or alkaline technology, solved since Ni when on Zn-Ni alloy, depositing the Zn in the Zn-Ni coating in the Ni plating bath, dissolve the bad problem of bonding force that causes.
(4) adopt this compositional modulation Zn-Ni/Ni or Ni/Zn-Ni multilayer film technology, improved the solidity to corrosion of coating.Compare with single Zn, the Zn-Ni alloy coating of same thickness, solidity to corrosion improves.
(5) good through the bonding force of the coating in thermal shock experiment and the scratch experiment proof multilayer film and coating, coating and matrix.
Description of drawings
Fig. 1 is preparation method's schema of the present invention;
Fig. 2 adopts Zn-Ni/Ni multilayer film that the inventive method the prepares metallograph at 1000 times of following microscopic appearances.
Embodiment
The multilayer film preparation method of admiro provided by the invention and nickel combination, preparation flow as shown in Figure 1, concrete implementation step is as follows:
The first step, preparation alkaline wash, pickle solution and electroplate liquid.
Alkaline wash is to contain NaOH, Na
3PO
412H
2O, Na
2CO
310H
2O, Na
2SiO
3NH
2The aqueous solution of O wherein contains NaOH 60～80g, Na in every liter of alkaline wash
3PO
412H
2O 20～40g, Na
2CO
310H
2O20～40g, Na
2SiO
3NH
2O 20～40g, all the other are water.
Pickle solution adopts HCl solution, and to contain HCl in every liter of pickle solution be 4～8mL.
Alkalescence Zn-Ni alloy electroplating liquid is for containing ZnO, NiSO
4, NaOH, complexing agent, additive and brightening agent the aqueous solution, in every liter of plating bath, contain ZnO 10～30g, NiSO
45～13g, NaOH 100～140g contains an amount of complexing agent, additive and brightening agent and water in addition.
Described complexing agent is made up of two or more the material in ammonium citrate, trolamine, quadrol, diethylenetriamine, tetraethylene pentamine, Seignette salt, EDTA and the ammoniacal liquor.The complexing agent components contents of required interpolation in plating bath is (containing in every liter of plating bath): ammonium citrate 5～40g or trolamine 38～80mL or quadrol 25～40mL or diethylenetriamine 3～20mL or more than the tetraethylene pentamine 3mL or among Seignette salt 15～25g or EDTA 8～15g or the ammoniacal liquor 10～20mL two kinds or two or more.
Described additive is the mixture of any one and DE among phytic acid or sodium phytate or the CTAB.The content of the binder component of required interpolation is (containing in every liter of plating bath) in plating bath: phytic acid 0.05～15mL or sodium phytate 0.1～5g or CTAB 0.1～5g and DE 1.5～15mL.
Described brightening agent is one or more in ZB, vanillin food grade,1000.000000ine mesh, thiocarbamide, three kinds of materials of asccharin.The brightening agent content that needs in every liter of plating bath to add is (containing in every liter of plating bath): one or more among ZB 1～10mL or vanillin food grade,1000.000000ine mesh 0.2～2g or thiocarbamide 1～2g or the asccharin 1～5g.
The electroplate liquid of electroplated Ni mainly is made up of main salt and complexing agent.Described main salt is NiSO
4And NiCl
2In one or both.The content that needs main salt in the plating bath is (containing in every liter of plating bath): NiSO
4100～350g or NiCl
2Among 10～300g one or both.Described complexing agent is to be made up of two or more the material in ammonium citrate, Trisodium Citrate, citric acid, ammoniacal liquor, trisodium phosphate, potassium pyrophosphate and the trolamine.The complexing agent components contents of required interpolation in plating bath is (containing in every liter of plating bath): ammonium citrate 40～60g, perhaps Trisodium Citrate 150～200g, perhaps citric acid 10～30g, perhaps ammoniacal liquor 30～150ml, perhaps trisodium phosphate 40～100g, perhaps potassium pyrophosphate 50～150g, perhaps two kinds among trolamine 10～40ml or two or more.Other added ingredientss are one or more in ammonium sulfate, sodium-chlor, sal epsom, the S-WAT.
The content that also contains added ingredients in plating bath is (containing in every liter of plating bath): ammonium sulfate 40～60g, and sodium-chlor 10～30g, sal epsom 10～60g is on one or more among S-WAT 5～20g.
In second step, mechanical grinding is cleaned plating piece.
Plating piece is carried out mechanical grinding successively on aluminum oxide sandpaper, clean with organic solvent or aqueous cleaning agent then.Described organic solvent or aqueous cleaning agent are used to remove the greasy dirt of matrix surface, and organic solvent can be chosen trichloroethane, gasoline, and acetone, ethanol, trieline, a kind of arbitrarily in the tetracol phenixin, and adopt more than the ultrasonic cleaning matrix surface 10min.
The 3rd step, alkali cleaning.
The alkaline wash that plating piece after second step cleaned immerses the first step preparation carries out alkali cleaning, and the temperature of alkali cleaning is 70～90 ℃, behind time 10～20min with plating piece successively via mobile hot water wash, mobile cold wash;
The 4th step, pickling.
To carry out pickling through the plating piece after the 3rd step alkali cleaning, 15～30 ℃ of pickle solution temperature, scavenging period 0.5～1.0min takes out after the via flow cold wash.
In the 5th step, electroplate.
The multilayer film of electroplated zinc nickel alloy and nickel combination comprises electroplating Zn-Ni alloy coating and Ni coating, and wherein the concrete steps of electroplating Zn-Ni/Ni multilayer film are as follows:
(a) will be immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the first step through the 4th plating piece of step after the pickling and electroplate, electroplate after washing.The condition of electroplating Zn-Ni alloy coating is current density 1～6A/dm
2, 10～35 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the plating bath of the electroplated Ni for preparing in the step 1, then washing.The condition of electroplated Ni coating is current density 0.5～3.0A/dm
2, pH value 7～9,25～65 ℃ of temperature.
(c) repeating step (a) and (b) satisfy the multiplicity requirement up to the Zn-Ni/Ni multilayer film, dry up coating at last.
The concrete steps of electroplated Ni/Zn-Ni multilayer film are as follows:
(a) will be immersed in the Ni electroplate liquid for preparing in the first step through the 4th plating piece of step after the pickling and electroplate, electroplate after washing.The condition of electroplated Ni coating is current density 0.5～3.0A/dm
2, pH value 7～9,25～65 ℃ of temperature.
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the step 1, then washing.The condition of electroplating Zn-Ni alloy coating is current density 1～6A/dm
2, 10～35 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.
(c) repeating step (a)～(b) satisfies the multiplicity requirement up to the Ni/Zn-Ni multilayer film, dries up coating at last.
To the Zn-Ni/Ni that obtains after electroplating or Ni/Zn-Ni coating carries out pattern and performance analysis shows, the coating surface smooth.The dark plating and the covering power of plating bath are good.Neutral salt spray test shows, adopts this compositional modulation Zn-Ni/Ni or Ni/Zn-Ni multilayer film to compare with single Zn, the Zn-Ni alloy coating of same thickness, and solidity to corrosion improves.Bonding force through the coating in thermal shock experiment and the scratch experiment proof multilayer film and coating, coating and matrix is good.Wherein the nickel content of zn-ni alloy deposits is 10%～15%, and coating is single γ phase; The current efficiency height of negative electrode reaches 80～90%.
The modulation wavelength of compositional modulation alloy Zn-Ni/Ni multilayer film is by galvanized time or current density decision, and the number of plies of multilayer film is decided by Zn-Ni coating and Ni coating alternate frequency.
Neutral salt spray test adopts 5% the sodium chloride salt aqueous solution, and the solution pH value is transferred at the solution of neutral range (6～7) as spraying usefulness, and test temperature is all got 35 ℃, and the rate of descent that requires salt fog is between 1～2mL.
Scratch test is that the hard that adopts a cutting edge to wear into 30 ° of acute angles is drawn cutter, and drawing the length of side is the square lattice of 1mm, and whether the coating of observing in the grid peels off from matrix.During line, should impose enough pressure, make a stroke cutter once just can scratch coating and reach matrix metal.If the coating in the cut district has any part to break away from, think that then bonding force is bad, if do not break away from, description taken in conjunction power is good.
Thermal shock test is sample to be placed on be heated to 190 ± 10 ℃ in the stove, and time 0.5h puts into the room temperature water quenching then, and triplicate checks whether coating bubbles, comes off.If have foaming, obscission description taken in conjunction power bad, if do not bubble, obscission description taken in conjunction power is good.
Embodiment one:On the 30CrMnSiA steel matrix, electroplate Zn-Ni/Ni and Ni/Zn-Ni multilayer film.
The first step, preparation alkaline wash, pickle solution and electroplate liquid.
Contain in every liter of alkaline wash: NaOH 70g, Na
3PO
412H
2O 30g, Na
2CO
310H
2O 30g, Na
2SiO
3NH
2O 30g.All the other are water.
Contain HCl 6mL in every liter of pickle solution.
Every liter of Alkaline Zinc boron-tungsten-iron-nickel alloy electroplating contains: ZnO 10g, NiSO
45g, NaOH 120g, complexing agent tetraethylene pentamine 3mL, trolamine 38mL, ammoniacal liquor 10mL, additive DE 1.5mL, CTAB 2g, brightening agent ZB3mL, vanillin food grade,1000.000000ine mesh 0.2g, all the other are water.
The plating bath of electronickelling contains for every liter: single nickel salt 150g, and Trisodium Citrate 200g, nickelous chloride 10g, trolamine 20ml, sal epsom 40g, all the other are water.
In second step, mechanical grinding is cleaned plating piece.
Plating piece is carried out mechanical grinding successively on aluminum oxide sandpaper, clean with organic solvent or aqueous cleaning agent then.Described organic solvent or aqueous cleaning agent are used to remove the greasy dirt of matrix surface, and organic solvent can be chosen trichloroethane, gasoline, and acetone, ethanol, trieline, a kind of arbitrarily in the tetracol phenixin, and adopt more than the ultrasonic cleaning matrix surface 10min.
The 3rd step, alkali cleaning.
The alkaline wash that plating piece after second step cleaned immerses the first step preparation carries out alkali cleaning, and the temperature of alkali cleaning is 70～90 ℃, behind time 10～20min with plating piece successively via mobile hot water wash, mobile cold wash;
The 4th step, pickling.
To carry out pickling through the plating piece after the 3rd step alkali cleaning, 15～30 ℃ of pickle solution temperature, scavenging period 0.5～1.0min takes out after the via flow cold wash.
In the 5th step, electroplate.
Plating comprises electroplated zinc nickel alloy and nickel alloy coating, and electroplating Zn-Ni/Ni multilayer film concrete steps are as follows:
(a) will be immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the first step through the 4th plating piece of step after the pickling and electroplate, electroplate after washing.The condition of electroplating Zn-Ni alloy coating is current density 1A/dm
2, 10 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the plating bath of the electroplated Ni for preparing in the step 1, then washing.The condition of electroplated Ni coating is current density 1A/dm
2, pH value 7,25 ℃ of temperature.
(c) repeating step (a) and (b) satisfy the multiplicity requirement up to the Zn-Ni/Ni multilayer film, dry up coating at last.
Electroplated Ni/Zn-Ni multilayer film concrete steps are as follows:
(a) will be immersed in the Ni electroplate liquid for preparing in the first step through the 4th plating piece of step after the pickling and electroplate, electroplate after washing.The condition of electroplated Ni coating is current density 1A/dm
2, pH value 7,25 ℃ of temperature.
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the alkaline Zn-Ni alloy electroplating liquid for preparing in the step 1, then washing.The condition of electroplating Zn-Ni alloy coating is current density 1A/dm
2, 10 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more.
(c) repeating step (a)～(b) satisfies the multiplicity requirement up to the Ni/Zn-Ni multilayer film, dries up coating at last.
Different coating and operational condition are investigated, and its result is as shown in table 1.
Different coating of table 1 and operational condition are to the influence of coating performance
Annotate:
*Expression sublayer thickness/multilayer coating total thickness.1/8 expression sublayer thickness is that every layer thickness is 1 μ m, and the multilayer film total thickness is 8 μ m.
The Zn-Ni/Ni multilayer film that obtains after the plating, its surfacing light, show by the solidity to corrosion salt-fog test in the table 1, Zn coating red rust occurs at 450h, Zn-Ni alloy coating red rust occurs at 1632h, all be better than single Zn, the Zn-Ni alloy coating of same thickness and Zn-Ni/Ni still is the solidity to corrosion of Ni/Zn-Ni multilayer coating, and be better than the Zn-Ni/Ni multilayer film from the solidity to corrosion that sample 3 and 4 experimental result can draw sublayer thickness Ni/Zn-Ni multilayer film when identical.This is because Ni is making the corrosion cell that easily forms big negative electrode primary anode outermost the time, thus the easier generation of corrosion.As can be seen when the total thickness of coating all is 8 μ m, sublayer thickness is that the corrosion resisting property of multilayer film of 2 μ m is best by the experimental result of sample 4,5,6.This is because the alternative number of plies is many more, Cl
-Penetrating whole coating, to reach matrix difficult more, and the matrix generation corrosive time is late more, but when the thickness of sublayer too thin, compactness is bad, the hole is more, causes corrosion resisting property to descend to some extent.By the experimental result of sample 5,7,8 as can be seen the size of current density also can influence the solidity to corrosion of coating.Current density during plating is crossed the compactness reduction that conference causes coating, has caused solidity to corrosion decline.Bonding force through the coating in thermal shock experiment and the scratch experiment proof multilayer film and coating, coating and matrix is good.Wherein the nickel content of zn-ni alloy deposits is 12.4%, and coating is single γ phase; The current efficiency height of negative electrode reaches 81～84%.
Embodiment two:At the stainless steel base sugared Ni/Zn-Ni multilayer film that powers on.
The first step, preparation alkaline wash, pickle solution and electroplate liquid.
The preparation of alkaline wash and pickle solution is with embodiment one.
The plating bath of electroplated zinc nickel alloy is ZnO, NiSO
4, the aqueous solution formed of NaOH, ammonium citrate, tetraethylene pentamine, trolamine, EDTA, phytic acid, DE, thiocarbamide, and contain in every liter of Alkaline Zinc boron-tungsten-iron-nickel alloy electroplating: ZnO 20g, NiSO
410g, NaOH 100g, complexing agent ammonium citrate 15g, tetraethylene pentamine 20mL, trolamine 40mL, EDTA 15g, additive phytic acid 0.15mL, DE 9mL, brightening agent thiocarbamide 1g, all the other are water.
Every liter of electronickelling plating bath contains: single nickel salt 100g, and potassium pyrophosphate 75g, citric acid 15g, ammoniacal liquor 50mL, all the other are water.
In second step, in the 3rd step, the 4th step is with example one.
In the 5th step, electroplate.
Step is: electroplated Ni → washing → electroplating Zn-Ni alloy → washing → electroplated Ni → washing → electroplating Zn-Ni alloy → wash → dry up.
Wherein, the operational condition of electroplating Zn-Ni alloy is 2A/dm
2, 10min, 20 ℃.
The operational condition of electroplated Ni is 2A/dm
2, 5min, 9,40 ℃ of pH values.
The Ni/Zn-Ni multilayer film that obtains after the plating, its surfacing light, every layer of Zn-Ni alloy coating or Ni thickness of coating are about 2 μ m, be that multilayer film thickness is about 8 μ m and 8 μ m thick single Zn, Zn-Ni alloy coating and compares, solidity to corrosion improves, and its neutral salt spray test shows that Zn coating red rust occurs at 450h, Zn-Ni alloy coating red rust occurs at 1632h, and this Ni/Zn-Ni multilayer film red rust occurs at 2112h.Bonding force through the coating in thermal shock experiment and the scratch experiment proof multilayer film and coating, coating and matrix is good.Wherein the nickel content of zn-ni alloy deposits is 13.1%, and coating is single γ phase; The current efficiency height of negative electrode reaches 87.8%.
Embodiment three:On the copper matrix, electroplate the Zn-Ni/Ni multilayer film.
The first step, preparation alkaline wash, pickle solution and electroplate liquid.
Preparation alkaline wash, pickle solution are with embodiment one.
The Alkaline Zinc boron-tungsten-iron-nickel alloy electroplating is ZnO, NiSO
4, the aqueous solution formed of NaOH, Seignette salt, tetraethylene pentamine, trolamine, sodium phytate, DE, asccharin, and in every liter of basic plating admiro plating bath, contain ZnO 30g, NiSO
413g, NaOH 140g, complexing agent Seignette salt 20g, tetraethylene pentamine 20mL, trolamine 80mL, additive sodium phytate 0.15g and DE 15mL, brightening agent asccharin 1g, all the other are water.
The plating bath of electronickelling contains for every liter: single nickel salt 350g, and ammonium citrate 40g, trolamine 10ml, ammoniacal liquor 80ml, all the other are water.
In second step, in the 3rd step, the 4th step is with example one.
In the 5th step, electroplate.
Step is: electroplating Zn-Ni alloy → washing → electroplated Ni → washing → electroplating Zn-Ni alloy → washing → electroplated Ni → wash → dry up.
Wherein, the operational condition of electroplating Zn-Ni alloy is 3A/dm
2, 5min, 20 ℃.
The operational condition of electroplated Ni is 3A/dm
2, 3min, 8,65 ℃ of pH values.
The Zn-Ni/Ni multilayer film that obtains after the plating, its surfacing light, every layer of Zn-Ni alloy coating or Ni thickness of coating are about 2 μ m, be that multilayer film thickness is about 8 μ m and 8 μ m thick single Zn, Zn-Ni alloy coating and compares, solidity to corrosion improves, and its neutral salt spray test shows that Zn coating red rust occurs at 450h, Zn-Ni alloy coating red rust occurs at 1632h, and this Ni/Zn-Ni multilayer film red rust occurs at 1844h.Compare with the single Zn coating of same thickness, solidity to corrosion has improved 5 times.Bonding force through the coating in thermal shock experiment and the scratch experiment proof multilayer film and coating, coating and matrix is good.Wherein the nickel content of zn-ni alloy deposits is 13.6%, and coating is single γ phase; The current efficiency height of negative electrode reaches 85.4%.
More examples see Table 2.
Table 2 embodiment four～eight
Claims (7)
1, the method for the multilayer film of electrochemical deposition component modulation admiro and nickel combination is characterized in that comprising:
The first step, preparation alkaline wash, pickle solution and electroplate liquid;
In second step, mechanical grinding is cleaned plating piece;
The 3rd step, alkali cleaning;
The 4th step, pickling;
In the 5th step, electroplate;
Described electroplate liquid comprises alkaline Zn-Ni alloy electroplating liquid of configuration and Ni electroplate liquid, and wherein the electroplate liquid of electroplated Ni is neutral or alkaline, mainly is made up of main salt and complexing agent, and described main salt is NiSO
4And NiCl
2In one or both; Described complexing agent is to be made up of two or more the material in ammonium citrate, Trisodium Citrate, citric acid, ammoniacal liquor, trisodium phosphate, potassium pyrophosphate and the trolamine;
Described plating comprises electroplating Zn-Ni alloy coating and Ni coating, and concrete steps are as follows:
(a) will in the 4th plating piece of step after the pickling be immersed in the electroplate liquid of the alkaline Zn-Ni alloy for preparing in the first step or Ni, electroplate, electroplate after washing;
(b) plating piece after the washing in the above-mentioned steps (a) is immersed in the plating bath of the electroplated Ni for preparing in the step 1 or Zn-Ni alloy and electroplate, electroplate after washing;
(c) repeating step (a)～(b) satisfies the multiplicity requirement up to Zn-Ni/Ni or Ni/Zn-Ni coating, dries up coating at last.
2, the method for the multilayer film of electrochemical deposition component modulation admiro according to claim 1 and nickel combination, it is characterized in that: alkaline wash is to contain NaOH, Na
3PO
412H
2O, Na
2CO
310H
2O, Na
2SiO
3NH
2The aqueous solution of O wherein contains NaOH 60～80g, Na in every liter of alkaline wash
3PO
412H
2O 20～40g, Na
2CO
310H
2O 20～40g, Na
2SiO
3NH
2O 20～40g, all the other are water;
Described pickle solution adopts HCl solution, and to contain HCl in every liter of pickle solution be 4～8mL.
3, the method for the multilayer film of electrochemical deposition component modulation admiro according to claim 1 and nickel combination, its feature
Be: the content that needs main salt in the electroplate liquid of electroplated Ni is to contain in every liter of plating bath: NiSO
4100～350g or NiCl
2Among 10～300g one or both.
4, the method for the multilayer film of electrochemical deposition component modulation admiro according to claim 1 and nickel combination, it is characterized in that: the complexing agent components contents of required interpolation in the plating bath of electroplated Ni is to contain in every liter of plating bath: ammonium citrate 40～60, perhaps Trisodium Citrate 150～200g, perhaps citric acid 10～30g, perhaps ammoniacal liquor 30～150ml, perhaps trisodium phosphate 40～100g, perhaps potassium pyrophosphate 50～150g, perhaps two kinds among trolamine 10～40ml or two or more.
5, modulate the method for the multilayer film of admiro and nickel combination according to the described electrochemical deposition component of claim 1～4, it is characterized in that: also contain in other added ingredients ammonium sulfate, sodium-chlor, sal epsom, the S-WAT one or more in the electroplate liquid of described electroplated Ni, and in every liter of plating bath, contain: ammonium sulfate 40～60g, sodium-chlor 10～30g, sal epsom 10～60g, one or more among S-WAT 5～20g.
6, the method for the multilayer film of electrochemical deposition component modulation admiro according to claim 1 and nickel combination, it is characterized in that: the condition of electroplated Ni coating is current density 0.5～3A/dm
2, pH value 7～9,25～65 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more; Under the constant condition of other processing condition, galvanized current density is big more, and thickness of coating is thick more.
7, the method for the multilayer film of electrochemical deposition component modulation admiro according to claim 1 and nickel combination, it is characterized in that: alkaline Zn-Ni alloy electroplating liquid is for containing ZnO, NiSO
4, NaOH, complexing agent, additive and brightening agent the aqueous solution, in every liter of plating bath, contain ZnO 10～30g, NiSO
45～13g, NaOH 100～140g contains an amount of complexing agent, additive and brightening agent and water in addition; The condition of electroplating Zn-Ni alloy coating is current density 1～6A/dm
2, 10～35 ℃ of temperature, under the constant condition of other processing condition, electroplating time is long more, and thickness of coating is thick more; Under the constant condition of other processing condition, galvanized current density is big more, and thickness of coating is thick more.
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